油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
10 巻 , 12 号
選択された号の論文の11件中1~11を表示しています
  • 立石 悌三郎, 藤原 正雄, 村瀬 幸市
    1961 年 10 巻 12 号 p. 717-720
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    In preparing the cacao butter like fat from palm oil, two methods were investigated, one merely by fractional crystallization and the other fractional crystallization after hydrogenation. The qualities of the products by the above two methods were compared to with that of cacao butter, which resulted as follows.
    The yield of cacao butter like fat from palm oil was 15 per cent, which was obtained by eliminating higher and lower melting fractions through twice fractional crystallization using methyl ethyl keton as solvent. For the purpose of increasing yield, the fractional crystallization of hydrogenated palm oil was investigated. After testing selective and nonselective conditions of hydrogenation, we obtained the cacao butter like fat of good quality from the palm oil hydrogenated under selective condition and through twice fractional crystallization from methyl ethyl keton. The yield was 20 per cent.
    The cacao butter like fat thus obtained showed no melting point lowering when mixed with cacao butter, and we confirmed that the qualities on melting point, softening point, and on solid content index were satisfactory.
  • 中里 敏
    1961 年 10 巻 12 号 p. 721-723
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Topped tall oil (bp less than about 200°C/5mmHg) obtained by distillation of crude tall oil contains much unsaponifiable matter and has been fewly utilized because of its offensive odor and dark color.
    Three kinds of tall oil samples, the topping oil, the neutral oil from topping oil by removing acidic components, the decolored oil obtained from neutral oil by pressurized hydrogenation, were maleinized at 180°C, then esterified with various alcohols. These products were examined for drying time and for other properties to obtain good dryness as paint raw material.
    The neutral oil has lighter color than the original topping oil, and the decolored oil has lighter color than the neutral oil.
    There were little differences in iodine values and reactivity to the maleic anhydride between the neutral oil and the decolored oil.
    The esterification of maleinized oils was difficult with monohydric alcohols, but was easy with polyhydric alcohols. In the case of pentaerythritol it tends to gel.
    The glycerine esters of maleinized neutral oil and maleinized decolored oil had excellent drying properties.
    As a result, the topping oil can be utilized as raw materials for paints, by removing acid component from it, reduction for decoloring if necessary, maleinization and esterification with polyhydric alcohols.
  • 宮川 高明, 野水 英男
    1961 年 10 巻 12 号 p. 724-727
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Highly unsaturated fatty acid esters carrying more than 4 nonconjugated double bonds changed their structure to the conjugated polyene form, when heated under interruption of air.
    The compounds produced by heating at 200°C without solvent were linear and had the cis-cis-trans conjugated triene form showing absorption maxima at 266, 277 and 287.5mμ, whereas those prepared by treating at 215°C together with 10 times of microcrystalline wax consisted both of the linear and of the ring compounds, in nearly the same proportion.
    In both cases, the conjugated triene compounds were all monomeric and the dimeric triene was never found.
    When heated at 250°C without solvent the produced conjugated diene had the absorption maximum at 236mμ and consisted mainly of the dimeric compounds having the cyclohexane ring structure.
    In contrast, the compounds treated at 250°C with microcrystalline wax included not only the dimeric conjugated diene, above described, but also the monomeric diene that may have the polycyclic form as well as cyclohexane ring in about the same ratio.
    Polymer more than dimer was scarcely found under our experimental conditions.
  • 福島 正敏
    1961 年 10 巻 12 号 p. 727-733
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    For purpose of clarifying the fundamental reaction conditions, in expected case of commercial reaction of castor oil, the reaction of methyl ricinoleate with metallic sodium was investigated. Some derivatives of the raw ester, such as ricinoleic acid, polyester, reductive condensation products and ricinoleyl alcohol were detected in the reaction products. Based on these products and hydrogenation rate, the reactivity of OH-group was investigated and further the practical condition of Bouveault et Blanc reduction was predicted.
    When methyl ricinoleate was reduced by using tertiary amylalcohol and methylisobutyl carbinol as the reducing alcohol, the change in yield of ricinoleyl alcohol was determined with increase in ƒvalue (………… relating to mole ratio, total OH-group mole/reducing alcohol mole). The quantity of reducing alcohol required for maximum yield is consequently lower than the theoretical value of Bouveault et Blanc reduction of -COO-group.
    It was certified that a part of OH-group in the raw ester could possibly act as proton donor for reducing alcohol of low reactivity with sodium such as tertiary amylalcohol. Methyl ricinoleate could be reduced without formation of trans isomer, which was detected little by the infrared spectroscopy.
  • 福島 正敏
    1961 年 10 巻 12 号 p. 733-740
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Preparation and properties of fatty alcohols from natural glycerides and waxes were studied with the view to confirm industrialization of fat and oil reduction, being founded on methyl ester reduction inquired by idem.
    Investigating from the reaction of carboxyl group which will reflect on yields of fatty alcohols and other byproducts, the result of glyceride reduction was equivalent to that estimated from the methyl ester reduction. Higher alkyl esters such as sperm oil could be quantitatively reduced to produce fatty alcohols not accompanied with byproducts other than fatty acids. Fatty alcohols prepared by the reduction of natural glycerides and waxes were purified by means of distillation and liquid chromatography and identified for properties.
    The transition of double bonds was studied by ultraviolet spectroscopy in reference to the reduction of methyl esters.
  • 加藤 秋男, 土屋 知太郎
    1961 年 10 巻 12 号 p. 741-744
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Two kinds of high melting Point ferulates (mp 185.3186.5°C and 190.7191.7°C) as phenolic substances have been confirmed in the soapstock of rice bran oil. The formulas of these two ferulates have been established as same formula, C41H60O4.
    By saponification with alcoholic potassium hydroxide solution, these two ferulates have been converted into ferulic acid and two kinds of triterpenoid alcohols C31H52O having different melting points (170.5171.0°C and 179.4181.0°C).
  • 田川 清行, 飯野 重礼, 大庭 範秋
    1961 年 10 巻 12 号 p. 744-749
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    To study an emulsifying character of the 16 derivatives of polyoxyethylene-polyoxypropylene cetyl ethers, O/W emulsions of mineral oil, selected as the standard oil phase, were prepared for emulsification tests by using the combined emulsifiers which consist of these derivatives and the standard emulsifier, varying the rate of combination of two emulsifiers.
    (1) HLB values of these derivatives were determined from the optimum emulsifying condition. Increase in the mole numbers of propylene oxide, P, in a molecule showed a tendency to become smaller HLB values, however an abnormally high HLB values were observed for the derivatives which involved smaller number of moles of ethylene oxide, E, in a molecule and larger mole number of P.
    (2) The HLB value of these derivatives which gave the excellent O/W emulsions of mineral oil, being the HLB value at 10.2, was roughly between 914.
    (3) From the temperatures observed for the completion of phase inversion from W/O to O/W, the phase inversion temperature at optimum emulsification was higher when the mole number of P is smaller and that of E larger. For the derivatives having same mole number of E, the temperature generally became lower when the mole number of P becomes larger. Inclination of curve in the diagram, phase inversion temperature vs. combination of two emulsifiers, showed a tendency to decrease with increase of the mole number of P in a molecule.
  • 田川 清行, 飯野 重礼, 大庭 範秋
    1961 年 10 巻 12 号 p. 749-754
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Water titration method which is used for measuring the number of ml's of water (Water Number, or W.N.) required for making the system turbid by adding distilled water dropwise into a fixed quantity of a mixed solution of nonionic surfactant and solvent, was applied to several nonionic surfactants, such as those involving ester linkage, alkyl phenols, alkyl phenol-formalin resins and lower aromatic alcohols, and study was made for comparison of these samples.
    (1) Comparing the two mixed solvents, DB-4 (dioxane containing 4vol% benzene) and DB-10 (dioxane containing 10vol% benzene), the end point of titration for DB-10 was sharper than that of DB-4.
    (2) For naerly all of the nonionic surfactants, the water number increased linearly with increase of mole number (n) of ethoxy-unit in a molecule, and began to deviate from the linearity, and at last decreased gradually through the maximum. When n is above 100, there is a tendency for the water number to converge into a range from 10 to 12. (DB-10)
    (3) When the linear part of the curve is expressed as an equation, W.N.=A+Bn, the value of A decreases linearly against (log N) with increase of N (N : carbon number of the raw material). On the other hand, there was a general tendency for the value of B to become smaller with increase in N (DB-10).
  • 小山田 太一郎, 馬場 肇
    1961 年 10 巻 12 号 p. 754-758
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    In an attempt to prepare the improved water-repellents for cellulosic fabrics that are structually similar to reactive dyes of the Procion group, 2-hexadecyloxy-4, 6-dichloro-s-triazine and 2-octadecylamino-4, 6-dichloro-s-triazine were synthesized by the reaction of cyanuric chloride with sodium cetylate and by the reaction of 2-amino-4, 6-dichloro-s-triazine with octadecyl chloride, respectively. Both products exhibited duarable water-repellency when applied to cellulosic fabrics.
    On the other hand, some water-repellents of the Velan type were prepared from various hydroxy compounds bearing a hydrophobic group, such as monoglyceride, diglyceride, higher dialkylcarbinol, Guerbet's alcohol and tartarate, by treating with formaldehyde and hydrogen chloride and subsequently quaternizing with pyridine, and their water-repellencies were examined.
    Among the hydroxy compounds studied, the following ones gave water-repellent finishes : synthesized and commercial monostearins (1), synthesized distearin (2), dipentadecylcarbinol (3), diheptadecylcarbinol (4), 2-tetradecyloctadecanol-1 (5), a monoglyceride mixture (6) obtained by glycerolizing hydrogenated rapeseed oil, a mixture of dialkyl tartarates (7) prepared by esterifying tartaric acid with a mixture of cetyl alcohol and stearyl alcohol.
    Particularly the product prepared from the monoglyceride mixture 6 showed stronger water-repellency than the others, probably owing to the presence of a longer-chain hydrophobic group (C22). Apparently the forked structure of the products derived from the distearin 2, the carbinol 3 or 4, the Guerbet's alcohol 5 and the tartarate mixture 7 showed no improved water-repellent effect. There was no definite relation between the water-repellent effect of the above mentioned products and the surface tension or the penetrating power of their aqueous solution.
  • 永田 章, 根本 嘉郎, 酒井 善嗣, 木村 和三郎
    1961 年 10 巻 12 号 p. 759-761
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    Ampholytic surface active agents were investigated as dyeing assistants and antistatic agents in dyeing bath.
    Five carboxy-betaines, two sulfobetaines, sulfoether betaine, anionic surface active agents and nonionic surface active agents were used in the dyeing bath of acid dyes or dye chromium complex with nylon piece.
    Alkylamine carboxy-betaines showed excellent antistatic effect.
  • 中沢 君敏, 新谷 〓, 井室 素子
    1961 年 10 巻 12 号 p. 761-767
    発行日: 1961/12/20
    公開日: 2009/10/09
    ジャーナル フリー
    20 sample pieces of 1/4lb, 10 wrapped and the rest stripped, per each of 10 kinds of household margarine from market (8 domestic, and 2 American products) were prepared. Observation was made for 4 pieces of 1/4lb. 2 wrapped and the rest stripped, per each product, once in a month for 5 months in order to find out how the products change in moisture loss, rancidity, hydrolysis and appearance under such different conditions as surface and inner part, wrapping and bareness by measuring moisture, P.O.V., A.V. and color. With the lapse of time, the central part did not show any change, but the surface showed a drastic change in moisture. Aluminium foil was much better than parchment in retention of moisture. There was no difference between parchment and bareness. The effect of wrapping on halting the increase in P.O.V. was not recognized. Rancidity of margarine is rather an inner problem. Increase in A.V. is much influenced by operation of mold, but when there is no mold, there is little difference in A.V. increase between wrapping and bareness, surface and inner part. As to the color, it is darker in the inner part than the surface, and it fades slightly with the lapse of time. On the contrary, when surface became darker, the color increased with the lapse of time, and in this case the surface sometimes became darker than the inner part. The heavy coloration of surface was recognized to be happened by the oxidation of color.
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